Thiophosphoric acid amide esters

ABSTRACT

Thiophosphoric acid amide esters of the formula   wherein: R1 represents C1-C4-alkyl, R2 represents C1-C7-alkyl, C3-C5-alkenyl, C3-C5-alkynyl or unsubstituted oro substituted benzyl, R3 represents C1-C6-alkyl, allyl or C3-C6-cycloalkyl, R4 represents alkenyl, alkynyl, unsubstituted or substituted benzyl, phenethyl, phenyl or naphthyl, and X represents oxygen or sulphur, PROCESSES FOR THEIR MANUFACTURE AND THEIR USE IN PEST CONTROL.

United States Patent 11 1 Meyer et al.

1 1 Aug. 5, 1975 1 THIOPHOSPHORIC ACID AMIDE ESTERS [75] lnventors: Willy Meyer, Basel; Beat Biihner,

Binningen; Dag Dawes, Pratteln, all

[211 App]. No.: 394,704

[30] Foreign Application Priority Data Sept. 13. 1972 Switzerland 13458/72 July 9, 1973 Switzerland 9960/73 [52] U.S. Cl. 260/455 P; 260/207.1; 260/327 M; 260/3403; 260/938; 424/202; 424/211;

[51] Int. Cl..... C07c 155/08; C07f 9/24; AOln 9/36 [58] Field of Search 260/938, 455 P [56] References Cited FOREIGN PATENTS OR APPLICATIONS 18,119 8/1961 Japan 260/938 Primary Examiner-Anton H. Sutto Attorney, Agent, or FirmFrederick H. Rabin [57] ABSTRACT Thiophosphoric acid amide esters of the formula wherein:

R, represents C,C.,-alkyl,

R represents C -C -alkyl, C -C -alkeny1, C -,C,-,-alkynyl or unsubstituted oro substituted benzyl,

R represents c -C -alkyl, allyl or c C -cycloalkyl,

R, represents alkenyl, alkynyl, unsubstituted or substituted benzyl, phenethyl, phenyl or naphthyl, and

X represents oxygen or sulphur,

processes for their manufacture and their use in pest control.

10 Claims, No Drawings THIOPHOSPHORIC ACID AMlDE ESTERS The present invention relates to thiophosphoric acid amide esters, to processes for their preparation and to their use in pest control.

The thiophosphoric acid amide esters have the formula wherein:

R represents C C -alkyl,

R represents C C -alkyl, C -C -alkenyl, C -C alkynyl or unsubstituted or substituted benzyl, R represents C,C -alkyl allyl or C C -cycloalkyl,

R represents alkenyl, alkynyl, unsubstituted or substituted benzyl, phenethyl, phenyl or naphthyl, and

X represents oxygen or sulphur.

The alkyl, alkenyl and alkynyl groups denoted by R to R can be straight-chain or branched, unsubstituted or substituted, e.g. by halogen such as fluorine, chlorine, bromine and/or iodine, alkoxy, or alkylthio, The alkenyl and alkynyl groups in the case of R have chains containing 3-10, preferably 3-5, carbon atoms.

Examples of such groups are: methyl, methoxymethyl, methylthiomethyl, ethyl, chloroethyl, propyl, isopropyl, n-, i-, sec.-, tert.-butyl, n-pentyl, n-hexyl, nheptyl and their isomers, vinyl, allyl, 2-methallyl, propargyl and iso-butinyl. Where R denotes cycloalkyl, this is preferably cyclopropyl.

Preferred substituents on the benzyl, phencthyl, phenyl and naphthyl groups include halogen, preferably fluorine, chlorine and/or bromine, C C -alkyl, C -C haloalkyl, particularly CF C,C -alkoxy, C C,- alkylthio, C C -alkylsulphinyl, C C -alkylsulphonyl, C C -alkoxycarbonyl, C -;C ,-alkenyloxy, C C alkynyloxy, cyano, alkenyl, acetyl, OCH .CH-

and/or nitro.

Compounds of formula I preferred because of their effectiveness are compounds wherein R represents methyl or ethyl,

R represents C ,C =,-alkyl, allyl, propargyl or benzyl,

R represents C C -alkyl or allyl,

R rcpresents C C -alkenyl, C;;-C -alkynyl, benzyl or naphthyl, or phenyl unsubstituted, or monoor polysubstituted by methyl, alkoxy, methylthio, methylsulphinyl, methylsulphonyl, trifluoromethyl, fluorine, chlorine, bromine, ethyl, propyl, isopropyl, scc-butyl, C -C -alkenyl, nitro, propargyloxy, C ,C -alkoxycarbonyl,

SCH. z CH phenylazo, cyano, sulphonamido, acetyl, or -OCH CH O, and represents oxygen or sulphur.

Particularly preferred compounds of formula I are those wherein R represents methyl or ethyl,

R represents propyl, isopropyl, n-butyl, sec.-butyl,

iso-butyl, n-pentyl, propargyl, allyl or benzyl,

R represents methyl, propyl or allyl,

R represents allyl, propargyl, benzyl or naphthyl, or phenyl unsubstituted, or monoor poly-substituted by methyl, methoxy, methylthio, methylsulphinyl, methylsulphonyl, trifluoromethyl, fluorine, chlorine, bromine, ethyl, propyl, isopropyl, sec.-butyl,

nitro, propargyloxy, C C -alkenyl, C C,- alkoxycarbonyl,

/SCH2 CH s c H,'

phenylazo, cyano, sulphonamido, acetyl 0r X represents oxygen or sulphur.

Compounds of formula I more especially preferred,

however, are compounds wherein R represents ethyl,

R represents n-propyl, sec.-butyl, n-butyl, allyl, propargyl or benzyl,

R represents methyl or allyl,

R represents allyl, 'propargyl, or phenyl unsubstituted, or monoor poly-substituted by methyl, methoxy, methylthio, methylsulphinyl, methylsulphonyl, trifluoromethyl, fluorine, chlorine, bromine, ethyl, propyl, isopropyl, sec.-butyl, nitro, propargyloxy, allyl, methoxycarbonyl,

phenylazo, cyano, sulphonamido or acetyl, and X represents oxygen or sulphur. The compounds of formula I can be prepared by methods known per se, e.g. as follows:

In the formulae II to IX, R, to R, and X have the meanings given for formula I, Me stands for an alkali metal, particularly lithium, sodium or potassium, and Hal for fluorine, chlorine, bromine or iodine.

Suitable acid-binding agents are: tertiary amines, e.g. trialkylamines, pyridine, dialkylanilines; inorganic bases, such as hydrides, hydroxides; and carbonates and bicarbonates of alkali metals and alkaline-earth metals. The processes are performed at a reaction temperature of to 150C, under normal pressure and in solvents or diluents. Suitable solvents or diluents are, e.g. ethers and ethereal compounds, such as diethyl ether, dipropyl ether, dioxane, dimethoxyethane or tetrahydrofuran; amides such as N,N-dialkylated carboxylic acid amides; aliphatic, aromatic as well as halogenated hydrocarbons, particularly benzene, toluene, xylenes, chloroform or chlorobenzene; nitriles such as acetonitrile; DMSO, ketones such as acetone, methyl ethyl ketone and water.

The starting materials of formula 11 are in some cases known, or can be prepared by methods analogous, for exxample, to those described in the British Patent Specification No. 1,275,330. The active substances of formula I are suitable for the control of various animal and plant pests.

The said active substances possess nematocidal properties, and can be employed, for example, for the control of phytopathogenic nematodes. In some cases the active substances of formula I are suitable also as herbicides and plant regulating agents, as well as for the control of members of the division thallophyta, such as, e.g. of viruses, bacteria and of phytopathogenic fungi. They are effective in particular, however, against all development stages, such as eggs, larvae, nymphs, pupae, and adults of insects and members of the order acarina, such as mites and ticks.

The compounds of formula I can be used, for example, against the following insects or members of the order acarinazinsects of the families: Tettigonidae, Gryllidae, Gryllotalpidae, Blattidae, Reduviidae, Phyrrhocoridae, Cimicidae, Delphacidae, Aphididae, Diaspididae, Pseudococidae, Scarabaeidae, Dermestidae, Coccinellidae, Tenebrionidae, Chrysomelidae, Bruchidae, Tineidae, Noctuidae, Lymatriidae, Pyralidae, Gulicidae, Tipulidae, Stomoxydae, Trypetidae, Muscidae, Calliphoridae and Pulicidae; also acarids of the families: Ixodidae, Argasidae, Tetranychidae and Dermanyssidae. The insecticidal and/or acaricidal action can be substantially broadened and adapted to suit the given circumstances by the addition of other insecticides and/or acaricides. Suitable additives are, for example: organic phosphorus compounds; nitrophenols and their derivatives; formamidines; ureas; carbamates and chlorinated hydrocarbons.

The compounds of formula I can be used on their own or together with suitable carriers and/or additives. Suitable carriers and additives may be solid or liquid and they correspond to the substances common in formulation practice, such as, e.g. natural and regenerated substances, solvents, dispersing agents, wetting agents, adhesives, thickeners, binders and/or fertilisers.

For application, the compounds of formula I can be processed into the form of dusts, emulsion concentrates, granulates, dispersions, sprays or solutions, the formulation of these preparations being effected in a manner commonly known in practice. Also to be mentioned are cattle dips and spray races, in which aqueous preparations are used.

The agents according to the invention are prepared in a manner known per se by the intimate mixing and- /or grinding of active substances of formula I with suitable carriers, optionally with the addition of dispersing agents or solvents which are inert to the active substances. The active substances can be obtained and used in the following forms:

solid preparations: dusts, scattering agents, granulates, coated granulates, impregnated granulates and homogeneous granulates;

liquid preparations:

a. water dispersible active-substance concentrates:

wettable powders, pastes and emulsions; b. solutions.

The active substances of formula I can be formulated, for example, as follows:

Dusts The following substances are used for, the preparation of (a) a 5% dust, and (b) a 2% dust:

5 parts of active substance, parts of talcum;

2 parts of active substance, 1 part of highly dispersed silicic acid, 97 parts of talcum.

The active substances are mixed and ground with the carriers.

Granulate:

The following substances are used to produce a 5%, granulate:

5 parts of active substance,

0.25 parts of epichlorohydrin,

0.25 parts of cetyl polyglycol ether,

3.50 parts of polyethylene glycol,

91 parts of kaolin particle size 0.3 0.8 mm).

The active substance is mixed with epichlorohydrin and dissolved with 6 parts of acetone; the polyethylene glycol and cetyl polyglycol ether are then added. The solution thus obtained is sprayed on kaolin, and the acetone subsequently evaporated off in vacuo.

wettable powder:

The following constituents are used for the preparation of (a) a 40%, (b) and (c) a 25%, and (d) a 10% wettable powder:

40 parts of active substance,

5 parts of sodium lignin sulphonate,

1 part of sodium dibutyl-naphthalene sulphonate, 54 parts of silicic acid.

25 parts of active substance,

4.5 parts of calcium lignin sulphonate 1.9 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1), 7

1.5 parts of sodium dibutyl naphthalene sulphonate,

19.5 parts of silicic acid,

19.5 parts of Champagne chalk,

28.1 parts of kaolin.

7.5 parts of active substance, 2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol, 1.7 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1), 8.3 parts of sodium aluminium silicate, 16.5 parts of kieselguhr, 46 parts of kaolin.

parts of active substance,

3 parts of a mixture of the sodium salts of saturated fatty alcohol sulphates,

5 parts of naphthalenesulphonic acid/formaldehyde condensate,

82 parts of kaolin.

The active substances are intimately mixed, in suitable mixers, with the additives, the mixture being then ground in the appropriate mills and rollers. Wettable powders are pbtained which can be diluted with water to give suspensions of any desired concentration.

Emulsifiable concentrates The following substances are used to produce (a) a 10% and (b) a 25% emulsifiable concentrate:

10 parts of active substance,

3.4 parts of epoxidised vegetable oil,

13.4 parts of a combination emulsifier consisting of fatty alcohol polyglycol ether and alkylarylsulphonate calcium salt,

40 parts of dimethylformamide,

43.2 parts of xylene.

25 parts of active substance,

2.5 parts of epoxidised vegetable oil,

10 parts of an alkylarylsulphonate/fatty alcoholpolyglycol ether mixture 5 parts of dimethylformamide,

57.5 parts of xylene.

of C0,. The suspension is stirred for a further 15 hours at room temperature, then filtered and fully concentrated by evaporation.

The compound obtained is of the formula b. 25 g of N-(propylthio-ethoxyphosphoryl)-N- methylcarbamoyl chloride in 30 ml of abs. acetone is added dropwise at room temperature to a suspension of.

9.4 g of phenol and l 1.7 g of K CO in ml of abs. acetone. The suspension is stirred for 10 hours at 40C, then cooled and filtered. The filtrate, concentrated by evaporation, is purified by chromatography through silica gel.

The compound of the formula is obtained as a pale yellow liquid having a refractive index of n,, 1.5207.

EXAMPLE 2 Preparation of phenyl-N-(propargylthioethoxy-phosphoryl )-N- methylcarbamate A solution of 30.2 g of N-methyl-N-(QO- diethylthiophosphoryl)-phenylcarbamate and l 1.2 g of triethylenediamine in 100 ml of toluene is stirred overnight at 60C. An addition is made dropwise at ca. 40C (exothermic) of 8.2 g of propargyl chloride, and stirring subsequently continued overnight at 60C. The solution is diluted with 100 ml of petroleum ether and cleared by filtration.

The filtrate, concentrated by evaporation, is purified by chromatography through silica gel.

The compound of the formula 0 CH E CCH2S\H P is obtained as a pale yellow liquid having a refractive index of n 1.538. q

The following compounds are prepared in an analogous manner:

- Continued x ysical data 0 mF'=1.s035

0 n,f*=l,5330

m na a on HO cl-l,

CH3 CH3 CH, CH3

3 C li,

3 C l-l CH1 fCH-CH;

CH3 -CH -C E C Continued R1 R: R R4 X Physical data CH CH2=CHCH CH;. O 5

Cl CH3 CH- ,=CH-CH CH Q CH CH E C-CH; cu, 0

CI CH1, CH E c-cug CH 3 1:] O

CH3 CH C-CH; CH3 -CH2CH=CH2 o CH, CH C-CH; cri s CH3 CH3 Q 0 H3 CH3 'HC 5 c-cug 0 Cl o v I i ci cu, C -,H-,S CH=CHCH2-. 1 1: 0

EXAMPLE? and of gas. The test was carried out at 24C with 70% A. Insecticidal stomach poison action Cotton and potato plants were sprayed with a 0.05% aqueous active-substance emulsion (obtained from a emulsifiable concentrate) After the drying of the obtained coating, Spodoptera litoralis oro Heliothis virescens'larvae L; were placed onto the cotton plants, and Colorada beetle larvae (Leptinotarsa decemlineata) 'onto the potato plants. The test was carried out at 24C wi'th 60% relative humidity.

The compounds according to Examples 1 and 2 exhibited in the above test a good insecticidal stomach poison action against Spodoptera litoralis, Heliothis and Lcptinotarsa decemlineata larvae.

B. Systemic insecticidal action In order to determine the systemic action, rooted bean plants (Vicia faba) were plaeed'into a 0.01% aqueous activesubstance solution (obtained from a 10% emulsifiablc concentrate). After a period of 24 hours, bean aphids (Aphis fabae were placed onto the parts of the plants above the soil. The insects were protected by a special device from the effects of Contact relative humidity.

In-the above test, the compounds according to Examples l and 2 exhibited a systemic action against Aphis fabae.

EXAMPLE 4 Action against ticks A. Rhipicephalus bursa In each case, 5 adult ticks or 50 tick larvae were placed into a small glass test tube, and the test tubes then immersed for l to 2 minutes in 2 ml of an aqueous emulsion from a dilution series of 100, 10, l and 0.1 ppm of test substance. The tubes were then sealed with a standardised cotton plug, and inverted so that the ac- 'tive substance emulsion could be absorbed by the cot- Compounds according to Examples 1 and 2 were effective in these tests against adults and larvae of Rhipicephalus bursa and against sensitive and OP-resistant larvae, respectively, of Boophilus microplus.

EXAMPLE 5 Acaricidal action Phaseolus vulgaris (plants) were infested, 12 hours before the test for acaricidal action, with an infested piece of leaf from a mass culture of Tetranychus urticae. The transferred mobile stages were sprayed with -the emulsified test preparations from a chromotography-sprayer in a manner ensuring no running off of the spray liquor. An assessment was made after 2 to 7 days, by examination under a binocular, of the living and of the dead larvae, adults and eggs, and the results expressed in percentages. The treated plants were kept during the holding time in greenhouse compartments at 25C.

The compounds according to Examples 1 and 2 were effective in the above test against adults, larvae and eggs of Tetranychus urticae.

EXAMPLE 6 Action against soil nematodes In order to test the action against soil nematodes the active substances were added, in the concentration EXAMPLE 7 Action against Piricularia oryzae on Or'yzae saliva After being sprayed with a 0.05% suspension of the active substance made up as a wettable powder, young rice plants were, after drying of the applied coating, infested with a spore suspension of the fungus Piriarlaria orycae. After 3 days incubation time at 24C and with high relative humidity, an evaluation was made of the disease infestation compared with that in the case of infested but untreated control specimens. Compounds according to Examples 1 and 2 were effective in this test against Piricularia oryzae.

EXAMPLE 8 Virucidal action against potato-virus Y (PVY) and cucumber mosaic virus (CMV) Fifteen pepper plants (Capsicum annuum Var. California Wonder) per test were cultivated in a controlled-atmosphere cupboard under well standardised conditions; and, after development of the cotyledons, transplanted to a greenhouse; they were sprayed three days later with an aqueous emulsion containing 2000 ppm of the substance to be tested and, after a further 24 hours, mechanically inoculated.

The systemic symptoms of the virus infection appeared after one week, so that it is possible to determine the antiviral activity of the tested substances.

28 Compounds according to Examples l and 2 exhibited an antiviral action against potato-virus Y and cucumber-mosaic virus on pepper plants.

What we claim is: l. A compound of the formula wherein R represents C C, alkyl,

R represents C -C alkyl, C -C alkenyl, C -C alkenyl or benzyl,

R represents C C alkyl, allyl or C ;C cycloalkyl,

R represents C -C alkenyl, C -C alkynyl, benzyl, phenethyl, phenyl, naphthyl, or phenyl monoor poly-substituted by methyl, methoxy, methylthio, meth ylsulphinyl, methylsulphonyl, trifluromethyl, fluorine, chlorine, bromine, ethyl, propyl, isopropyl, sec.butyl, C -C alkenyl, nitro, propargyloxy, C C, alkoxycarbonyl, cyano, sulphonamido or acetyl, and

X represents oxygen or sulphur.

2. A compound according to claim 1, wherein R represents methyl or ethyl,

R represents C,-C,=, alkyl, allyl, propargyl or benzyl,

and

R represents C -C alkyl or allyl.

3. A compound according to claim 2, wherein R represents n-propyl, isopropyl, n-butyl, scc.butyl,

isobutyl, n-pentyl, propargyl, allyl or benzyl,

R represents methyl, n-propyl orally], and

R represents ally], propargyl, benzyl, naphthyl, phenyl or phenyl monoor polysubstituted by methyl, methoxy, methylthio, methylsulphinyl, methylsulphonyl, trifluoromethyl, fluorine, chlorine, bromine, ethyl, n-propyl, isopropyl, sec.butyl, nitro, propargyloxy, C -C alkenyl, C, -C, alkoxycarbonyl, cyano, sulphonamido or acetyl.

4. A compound according to claim 3, wherein,

R represents ethyl,

R representsm-propyl, sec.butyl, n-butyl, allyl, propargyl or benzyl,

R represents methyl or allyl, and

R represents allyl, propargyl, phenyl or phenyl monoor poly-substituted by methyl, methoxy, methylsulphinyl, methylsulphonyl, trifluoromethyl, chlorine, bromine, ethyl, n-propyl, isopropyl, sec.- butyl, nitro, propargyloxy, methoxycarbonyl, cyano, allyl, sulphonamido or acetyl. Y

I 5. Compound according to claim 4 of the formula a scam Q 29 30 7. Compound according to claim 3 of the formula 9. Compound according to claim 3 of the formula C] 0 u cu, ll OCN P SC ,H (n) OCN P sc m) (1 ll -l s Q 10. Compound according to claim 3 of the formula 8. Compound according to claim 3 of the formula I ll :11,, CH 3 O UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 898 260 Dated August 5 1975 II lnventofls) Willy Meyer, Beat Bohner & Dag Dawes It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Claim 5 the formula should appear as shown below:

(III-I3 SC1 H (n) O-C-N-P ll o o z s Signed and Sealed this thirtieth Day Of September 1975 [SEAL] Arrest."

RUTH C.'MASON C. MARSHALL DANN Arresting ()jficer (mnmissiniwr vflulenls and Trademarks FORM PO-105O (10-69) USCOMM-DC 60376-P69 u.s. GOVERNMENT PRINTING OFFICE: I969 l)366334 

1. A COMPOUND OF THE FORMULA
 2. A compound according to claim 1, wherein R1 represents methyl or ethyl, R2 represents C1-C5 alkyl, allyl, propargyl or benzyl, and R3 represents C1-C3 alkyl or allyl.
 3. A compound according to claim 2, wherein R2 represents n-propyl, isopropyl, n-butyl, sec.butyl, isobutyl, n-pentyl, propargyl, allyl or benzyl, R3 represents methyl, n-propyl or allyl, and R4 represents allyl, propargyl, benzyl, naphthyl, phenyl or phenyl mono- or polysubstituted by methyl, methoxy, methylthio, methylsulphinyl, methylsulphonyl, trifluoromethyl, fluorine, chlorine, bromine, ethyl, n-propyl, isopropyl, sec.butyl, nitro, propargyloxy, C3-C5 alkenyl, C1 -C4 alkoxycarbonyl, cyano, sulphonamido or acetyl.
 4. A compound according to claim 3, wherein, R1 represents ethyl, R2 represents n-propyl, sec.butyl, n-butyl, allyl, propargyl or benzyl, R3 represents methyl or allyl, and R4 represents allyl, propargyl, phenyl or phenyl mono- or poly-substituted by methyl, methoxy, methylsulphinyl, methylsulphonyl, trifluoromethyl, chlorine, bromine, ethyl, n-propyl, isopropyl, sec.butyl, nitro, propargyloxy, methoxycarbonyl, cyano, allyl, sulphonamido or acetyl.
 5. Compound according to claim 4 of the formula
 6. Compound according to claim 3 of the formula
 7. Compound according to claim 3 of the formula
 8. Compound according to claim 3 of the formula
 9. Compound according to claim 3 of the formula
 10. Compound according to claim 3 of the formula 